CA2209784A1 - An improved temperature compensated electrochemical gas sensor and method for closely tracking the temperature variations of a gas to be sensed - Google Patents
An improved temperature compensated electrochemical gas sensor and method for closely tracking the temperature variations of a gas to be sensedInfo
- Publication number
- CA2209784A1 CA2209784A1 CA002209784A CA2209784A CA2209784A1 CA 2209784 A1 CA2209784 A1 CA 2209784A1 CA 002209784 A CA002209784 A CA 002209784A CA 2209784 A CA2209784 A CA 2209784A CA 2209784 A1 CA2209784 A1 CA 2209784A1
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- Prior art keywords
- gas
- sensor
- temperature
- gas sensor
- thermistor
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- 238000000034 method Methods 0.000 title claims description 15
- 239000007789 gas Substances 0.000 claims abstract description 224
- 239000012528 membrane Substances 0.000 claims abstract description 28
- 239000003792 electrolyte Substances 0.000 claims abstract description 17
- 230000001934 delay Effects 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims description 43
- 230000008859 change Effects 0.000 claims description 20
- 239000012212 insulator Substances 0.000 claims description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 238000010349 cathodic reaction Methods 0.000 claims description 8
- 230000004044 response Effects 0.000 claims description 6
- 238000009792 diffusion process Methods 0.000 claims description 5
- 239000011244 liquid electrolyte Substances 0.000 claims description 5
- 238000012546 transfer Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims 1
- 238000009736 wetting Methods 0.000 claims 1
- SMNRFWMNPDABKZ-WVALLCKVSA-N [[(2R,3S,4R,5S)-5-(2,6-dioxo-3H-pyridin-3-yl)-3,4-dihydroxyoxolan-2-yl]methoxy-hydroxyphosphoryl] [[[(2R,3S,4S,5R,6R)-4-fluoro-3,5-dihydroxy-6-(hydroxymethyl)oxan-2-yl]oxy-hydroxyphosphoryl]oxy-hydroxyphosphoryl] hydrogen phosphate Chemical compound OC[C@H]1O[C@H](OP(O)(=O)OP(O)(=O)OP(O)(=O)OP(O)(=O)OC[C@H]2O[C@H]([C@H](O)[C@@H]2O)C2C=CC(=O)NC2=O)[C@H](O)[C@@H](F)[C@@H]1O SMNRFWMNPDABKZ-WVALLCKVSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000012937 correction Methods 0.000 description 2
- 230000003111 delayed effect Effects 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- 230000001627 detrimental effect Effects 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000011664 signaling Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/403—Cells and electrode assemblies
- G01N27/404—Cells with anode, cathode and cell electrolyte on the same side of a permeable membrane which separates them from the sample fluid, e.g. Clark-type oxygen sensors
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
- G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
- G01N27/14—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of an electrically-heated body in dependence upon change of temperature
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Analytical Chemistry (AREA)
- Physics & Mathematics (AREA)
- Electrochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Molecular Biology (AREA)
- Investigating Or Analyzing Materials By The Use Of Electric Means (AREA)
- Measuring Oxygen Concentration In Cells (AREA)
Abstract
An Electrochemical Gas Sensor having a temperature sensitive element such as a thermistor arranged within the gas sensor in a temperature insulative fashion for preventing any variations in the temperature of the applied gases to be sensed to be immediately conveyed to the temperature sensitive element thereby providing accurate temperature compensation signals to be combined with the generated sensor electrical output signals. The temperature sensitive element or thermistor is mounted in a heat sink to the expansion membrane of the gas sensor to be responsive only to changes in the temperature variations imparted by the sensor electrolyte and not by the variations in the temperature of the gas sensor body and associated elements thereby providing correct temperature compensation signals without error producing time delays.
Description
11,516 AN IMPROVED TEMPERATURE COMPENSATED ELECTROCHEMICAL
GAS SENSOR AND METHOD FOR CLOSELY TRACKING THE
TEMPERATURE VARIATIONS OF A GAS TO BE SENSED
Field of Invention This invention relates to electrochemical gas sensors for electrically signalling the concentration of an electrochemically active gas, such as oxygen, in a gas mixture and more part-icularly to improved apparatus and methods for closely tracking temperature variations of the gases applied to the gas sensor permitting accurate compensation for the temperature var-iations.
Backqround of Invention Electrochemical gas sensors are well known in the prior art for accurately detecting the concentration of an electro-chemically active gas, such as oxygen, in a gas mixture. The concentration of the gas is externally signalled by the elec-trical signal generated by the presence of the active gas that is oxidized or reduced at the surface of the gas sensing cathode electrode. The gas sensors comprise anode and cathode electrodes immersed in a pool of a liquid electrolyte. The electrical output signal from these gas sensors are in the form of an electrical current that corresponds to the partial pressure of the active gas being sensed. The current signal can be converted to a voltage signal by the mounting of a 11,516 2 1 suitable resistor across the output terminals of the gas sensor to derive a voltage signal in millivolts. Covnentionally, a printed circuit board is mounted to the gas sensor at the back side thereof with a suitable resistor thereon for providing 5 the voltage output signal. It is known that the gas sensor output signals are dependent on the temperature of the gas mixture applied thereto. The output signals from the sensors increase with an increase in the temperature of the applied gases. This change in output signal is due to the change in 10 the diffusion rate of the gas mixture through the input membrane for the gas sensor. At the higher temperatures, the electrical output signal increases due to the high diffusion rate of the gases through the input membrane for the gas sensor. As a result, the output signal increase results in an erroneous 15 output signal of the concentration of the gas sensed. To compensate the output signals for the temperature variations and provide accurate output signals, a suitable thermistor is conventionally mounted on the printed circuit board on the rear of the gas sensor. The thermistor provides an electrical output --20 signal for adjusting or compensating the sensor output signalfor the temperature variations in the applied gas. This enables the gas sensor to provide accurate measurements of the con-centrations of the sensed active gas at various temperatures without any addit~ional correction being required. These gas 25sensors have a sensing mem~rane at the front side for receiving the gas mixture to be analyzed. A pool of electrolyte is stored between the input sensing membrane and an expansion membrane.
The thermistor is spaced from the electrolyte. This prior art arrangement of the thermistor in gas sensors has been found to 30take a long time to equilibrate the changes in temperature of thegas mixture applied to the sensor in order to provide a temperature compensation signal. The thermistor in these prior art sensor arrangements is exposed to the gas indergoing analysis im-mediately upon application of the gas mixture to the sensor, 3swhile it takes 30-40 minutes for the sensor body to see a change 11,516 3 1 in the temperature of the applied gas mixture. As a result of this time delay there is an initial low reading due to the adjustment performed by the thermistor. This time delay may be on the order of 30 minutes to one hour. In medical applications wherein it is necessary to monitor the oxygen concentration given to a patient in a critical care unit, this delay may be too long and the error associated with the delayed temperature tracking could be up to lO per cent of the oxygen required by a patient and could be detrimental to the patient. Accordingly, there is a present need for an improved apparatus and method for more closely tracking and compensating a sensor electrical output signal for errors introduced by varying temperatures of the gas mixtures applied to the gas sensor to be analyzed.
Summary of Invention The present invention is an improved, more sensitive, electrochemical gas sensor having improved methods and means for tracking the temperature changes in the gases applied to the sensors for permitting the temperature compensation signals to be rapidly developed and utilized without any time delay, for providing correct, temperature compensated output signals and thereby accurate electrical output signals representative of the concentrations of the electrochemical active gases applied to the gas sensor to be analyzed. The above advantages are produced with small change in the cost of producing the improved gas sensor.
From a structural standpoint, the improved electro-chemical gas sensor includes thermistor means mounted adjacent to an expansion membrane, that is in contact with the gas sensor electrolyte and contains same, in a substantially thermal isolated relationship with respect to the temperature of the gases to be sensed conveyed to the gas sensor so that any change in the temperature of the gas to be sensed is not directly conveyed to the thermistor means whereby the gas sensor and the thermistor means both experience any change in CA 02209784 l997-07-08 11,516 4 1 temperature of the gas to be sensed at substantially the same time whereby said thermistor means provides electrical output signals in response to the sensed temperature changes in the gases being sensed without any substantial time delays between the temperature changes in the gases to be sensed and the electrical output signals provided by the thermistor means.
From a broad method standpoint, the present invention comprehends the provision of an electrochemical gas sensor to provide an electrical output signal in response to the app-lication of a gas mixture to the gas sensor having an electo-chemically active gas to be sensed therein due to the production of a cathodic reaction whereby the electrical output signal is representative of the concentration of the sensed electro-chemically active gas that varies with the temperatures of the gas mixtures thereby resulting in erroneous electrical output signals due to the temperature variations of the gas mixture, mounting thermistor means in the gas sensor in a preselected thermal insulative manner for minimizing any direct heat transfer to the thermistor means so that the gas sensor body and the thermistor means are exposed to the temperature variations of the gas mixture at essentially the same time for thereby permitting accurate compensation of the electrical output signals from the gas sensor, without any time delay, thereby providing accurate output signals of the concentrations of the sensed gases despite temperature variations in the applied gas mixtures.
The method includes the steps of mounting the thermistor means in a heat sink adjacent the gas sensor electrolyte and providing a plurality of thermal insulators stacked in the gas sensor with the thermistor means lead wires spiraled into coils and electrically accessible outside the gas sensor.
11,516 5 1 Brief Descri~tion of the Drawinqs These and other features of the present invention may be more fully appreciated when considered in light of the following specification and drawings, in which:
Fig. l is cross sectional view of a prior art electro-chemical gas senor having thermistor temperature compensation;
Fig. 2 is a graphical illustration of the gas sensor of Fig. 1 electrical output signal variations due to increased temperatures of the gas mixture applied to the gas sensor;
Fig. 3 is a cross sectional view of an electroche~ical gas sensor having means for closely tracking temperature variations of the gas mixtures applied to the gas sensor l-d embodying the present invention;
' Fig. 4 is a view from the top of an unpatted, th~r-istor, looking towards the back side of the gas sensor of Fig. 3 3:1 illustrating the spiral assembly of the thermistor leads, in part illustrated in dotted outline;
Fig. 5 is a side view of the thermistor arrange~en~ .~s viewed in Fig. 4;
Fig. 6 is a detached view of the top of the print.-d circuit board assembly as utilized in the gas sensor of Fi~. 3;
and Fig. 7 is a graphical illustration of the gas sensor of Figs. 3-6 electrical output signal variations due to the increase in the temperature of the gas mixture applied to the gas sensor.
11,516 6 1 Detailed Description of the Preferred Embodiment of the Invention An understanding of the problem of the present day organization of electrochemical gas sensors and the temperature compensation of the sensor electrical output signals by means of thermistor means leads to a better appreciation of the needfor the improvements disclosed herein and the benefits of the novel structures. The electrochemical gas sensor 10 is illustrated in Fig. 1 as a prior art galvanic type of gas sensor for prod-ucing a cathodic reaction at the gas sensing cathode electrode 12 for the gas sensor. The cathodic reaction is produced in response to gas mixtures applied to the gas sensor 10 when the cathode electrode 12 and the associated anode electrode 14 are wet by a suitable electrolyte 16 stored in the container 18 defining the body for the sensor 10. The electrolyte 16 has a preselected volume defined between the thin sensing membrane 20 and the expansion membrane 22 spaced on the opposite side of the anode electrode 14 from the cathode electrode 12. The back side of the container 18 is closed off by the provision of a printed circuit board 24 illustrated spaced from the membrane 22 and mounting a thermistor 26 and a plurality of resistors 28.
An electrical connector 30 is connected to the printed circuit board 24 for deriving the electrical output signals produced by the aforementioned cathodic reaction and'the thermistor signals to be combined for compensating for any temperature changes in the gas mixture applied to the gas sensor 10 in a well known manner. This structure is typical of the prior art galvanic type of electrochemical gas sensors capable of sensing the concentrations of electrochemically active gases, such as oxygen, in the gas mixtures applied to the gas sensor in parts per million. It should be recognized by those skilled in the art that the present invention is also applicable to other types of gas sensors including polarographic type gas sensors.
As illustrated in Fig. 1, the open end of the container 18 is illustrated with an open ended threaded member 32 for recei-ving the gas mixtures applied to the gas sensor 10. This 11,516 7 1 permitS the gas sensor lO to be threaded to a suitable gas block for receiving the gas mixtures flowing through to impinge against the sensing membrane 20. Such a gas block may be constructed of aluminum or plastic. The gas block is diagrammatically illustrated in dotted outline secured to the member 32 in Fig. l. Upon the application of the gas mixture to be analyzed to the gas sensor lO the concentration of the electrochemical active gas in the gas mixture produces a cathodic current that is due to the oxidation or reduction of the active gas providing an electrical current output signal from the sensor lO representative of the concentration of the active gas in the gas mixture. The electrical current can be converted to a voltage output signal by the provision of a suitable output resistor coupled across the output terminalsofthe sensor lO.
A ten ohm resistor mounted on the printed circuit board 24, for example will convert the autput currents to a voltage signal in millivolts. It is also well known that electrical output signals from the gas sensors lO are also dependent on the temp-erature and the temperature variations of the gas mixtures applied to the sensor. The electrical output signals increase in magnitude with the increases in the temperatures of the gas mixture being sensed or analyzed. This change in output signal - is due to the change in the diffusion rate of the applied gas through the thin sensing membrane 20. At the higher gas temp-eratures the output electrical signals increase due to the high diffusion rate of the applied gas through the sensing membrane 20 and thereby the derived output signals erroneously signal the concentration of the sensed active gas in the applied gas mixture. The prior art gas sensors utilized a temperature sensing device in the form of the thermistor 26 mounted on the printed circuit board 24 for the gas sensor lO to provide an electrical output signal representative of the temperature change in the applied gas to the gas sensor. The thermistor output siqnal is utilized as a temperature compensating signal for the erroneously generated sensor output signal to provide the correct 11,516 8 1 output signal compensated for the temperature variations, as well known, without the need for additional corrections.
The thermistor signals are utilized to cancel out the temp-erature components of the sensor generated signals in a known circuit manner. As can be appreciated from viewing Fig. l, the gas mixture to be analyzed is immediately exposed to the thermistor 26 and as a result signals a temperature change that produces an initial low, erroneous output signal from the gas sensor lO. It is known that the gas sensor body takes a time period on the order of 30-40 minutes to change in temperature before it will correctly signal the temperature change in the applied gas mixture. This time delay in pro-viding accurate electrical output signals has been found to be between 30 minutes to one hour. For a patient in a critical care unit wherein the supply of oxygen, for example, is mon-itored this time delay is excessive and the errors introduced with the delayed temperature tracking by the thermistor could be up to 10% of the required oxygen supply and could be detrimental to a patient.
The time delay introduced by the erroneous temperature tracking by the thermistor 26 for the gas sensor lO is graphically illustrated in Fig. 2 for a temperature change from 24 degrees centigrade to 40 degrees centrigade for tests con-ducted on three different gas sensors of the type of gas sensor lO. The space between the vertical lines in Fig. 2 represent 5 minutes in time. All three gas sensors signalled an immediate drop in the value of the electrical output signal due to the thermistor 26 being immediately exposed to the temperature change with a gradual increase in value as the sensor body absorbs the temperature change with time. The electrical output signal reaches asteady state condition after the time delay period required by the sensor body and associated elements to reach the changed temperature, in the above example the 40 de-grees C. This time delay period for the cells of Fig. 2 can be seen to be substantial, on the order of 30 minutes.
11,516 9 1 With the above prior art structures and problems in mind, the improved gas sensor lO' of the present invention will be examined in conjunction with the structures illustrated in Figs. 3-6 and the graphical representation of ~ig. 7. The basic structure of the galvanic type electrochemical gas sensor lO of Fig. l is illustrated in Fig. 3 but illustrating the improved arrangement for sensing the applied gas temperatures and tracking the temperatures without introducing the time delays of the prior art structures. The thermistor 26 in accordance with the present invention is located in very close proximity to the liquid electrolyte adjacent the expansion membrane 22 in a substantially thermally insulated relationship with the gas sensor body and the gases applied to the gas sensor lO' and thereby eliminates the prior art time delays involved in tracking the temperatures of the gases applied to the gas sensors during a change in the temperature of the gases.
To this end, the thermistor 26 is potted to the rear side of the expansion membrane 22 with a heat sink compound 34, such as a zinc oxide or silicone, as illustrated in Fig. 3. In this manner, any change in temperature of the gases undergoing analysis are not directly conveyed to the thermistor 26 to produce -erroneous signal outputs. The lead wires for the thermistor 26 comprise an electrically insulated cable 26C of approximately 3-4 inches in length having the individual lead 2S wires thereof secured to the printed circuit board 24 at the points "4" on the board; see Figs. 4 and 6.
Another important feature of the assembly of the thermistor 26 to the gas sensor 10' is the provision of thermal insulative means arranged between the heat sink compound 34 and the tops of the circuit board devices on the printed circuit board 24 as best illustrated in Figs. 3 and 5. The insulative means, as illustrated, comprises three individual layers of foam stacked upon one another between the heat sink 34 and the printed circuit board 24. The individual layers of foam in-sulation are each a different size and are identified in the 11,516 10 1 drawings as layers 36, 38 and 40 from the top to the bottom, see Fig, 5, in particular. The top most insulative layer 36 is positioned below the thermistor 26 and the heat sink compound 34 and is the smallest in size, diameter wise, of the three insulative layers. The bottom insulative layer 40 is the largest in diameter while the layer 38 is intermediate in size between the diameters of layers 36 and 40. The thickness of the three layers are essentially the same and in combination occupy the volume between the heat sink compound 34 and t!~-' printed circuit board 24. The three layers are arranged in ~
staggered relationship as best seen in Fig. 5. The insula~i~e cable 26C for the thermistor 26 is spiraled or coiled be~ n the insulative layers 36, 38 and 40 between the stacked ~ ~~s, see Figs. 3 and 4, and the individual lead wires of the _l~;e 26C
are connected to point "4" on the printed circuit board ~, as best seen in Fig. 4 and 6.
In the above described manner of insulatively sec_r:n~
the thermistor 26 any changeintemperature of the gas mixt_~s applied to the gas sensor 10' is not directly conveyed to ~e thermistor 26 since the gas sensor container or body 18 bo~
experience the change in gas temperature at essentially th~
same time. Therefore, the electrical output signals develc.-ed by the gas sensor 10' and the thermistor 26 when combined, correctly compensates the sensor generated electrical outp_t signals for the sensed temperature variations so that the resulting temperature compensated electrical output signals are true representations of the signals produced at the gas sensin~
cathode electrode, without any erroneous increases or decrel-,es due to temperature changes.
The gas sensor 10' was tested in the identical mann~?r as the sensor 10 and plotted in Fig. 7 for a temperature chan~e in the sensor applied gas from 24 degrees C. to 40 degrees C.
In Fig. 7, the output signals for six gas sensors are ill~ls~rated as coming to equilibrium right away, without any false incr?ases or decreases in electrical output signals as in the known --ior 11,516 1 art devices.
It should now be appreciated by those skilled in the gas sensor art that the present disclosure has advanced the art for precisely tracking the temperature changes in the gas mixtures applied to the gas sensor so as to provide more sensitive and accurately compensated electrical output signals that better track temperature changes. This tracking results due to the thermistor being responsive to the temperature changes imparted to the liquid electrolyte and not the temperature changes of the sensor body.
GAS SENSOR AND METHOD FOR CLOSELY TRACKING THE
TEMPERATURE VARIATIONS OF A GAS TO BE SENSED
Field of Invention This invention relates to electrochemical gas sensors for electrically signalling the concentration of an electrochemically active gas, such as oxygen, in a gas mixture and more part-icularly to improved apparatus and methods for closely tracking temperature variations of the gases applied to the gas sensor permitting accurate compensation for the temperature var-iations.
Backqround of Invention Electrochemical gas sensors are well known in the prior art for accurately detecting the concentration of an electro-chemically active gas, such as oxygen, in a gas mixture. The concentration of the gas is externally signalled by the elec-trical signal generated by the presence of the active gas that is oxidized or reduced at the surface of the gas sensing cathode electrode. The gas sensors comprise anode and cathode electrodes immersed in a pool of a liquid electrolyte. The electrical output signal from these gas sensors are in the form of an electrical current that corresponds to the partial pressure of the active gas being sensed. The current signal can be converted to a voltage signal by the mounting of a 11,516 2 1 suitable resistor across the output terminals of the gas sensor to derive a voltage signal in millivolts. Covnentionally, a printed circuit board is mounted to the gas sensor at the back side thereof with a suitable resistor thereon for providing 5 the voltage output signal. It is known that the gas sensor output signals are dependent on the temperature of the gas mixture applied thereto. The output signals from the sensors increase with an increase in the temperature of the applied gases. This change in output signal is due to the change in 10 the diffusion rate of the gas mixture through the input membrane for the gas sensor. At the higher temperatures, the electrical output signal increases due to the high diffusion rate of the gases through the input membrane for the gas sensor. As a result, the output signal increase results in an erroneous 15 output signal of the concentration of the gas sensed. To compensate the output signals for the temperature variations and provide accurate output signals, a suitable thermistor is conventionally mounted on the printed circuit board on the rear of the gas sensor. The thermistor provides an electrical output --20 signal for adjusting or compensating the sensor output signalfor the temperature variations in the applied gas. This enables the gas sensor to provide accurate measurements of the con-centrations of the sensed active gas at various temperatures without any addit~ional correction being required. These gas 25sensors have a sensing mem~rane at the front side for receiving the gas mixture to be analyzed. A pool of electrolyte is stored between the input sensing membrane and an expansion membrane.
The thermistor is spaced from the electrolyte. This prior art arrangement of the thermistor in gas sensors has been found to 30take a long time to equilibrate the changes in temperature of thegas mixture applied to the sensor in order to provide a temperature compensation signal. The thermistor in these prior art sensor arrangements is exposed to the gas indergoing analysis im-mediately upon application of the gas mixture to the sensor, 3swhile it takes 30-40 minutes for the sensor body to see a change 11,516 3 1 in the temperature of the applied gas mixture. As a result of this time delay there is an initial low reading due to the adjustment performed by the thermistor. This time delay may be on the order of 30 minutes to one hour. In medical applications wherein it is necessary to monitor the oxygen concentration given to a patient in a critical care unit, this delay may be too long and the error associated with the delayed temperature tracking could be up to lO per cent of the oxygen required by a patient and could be detrimental to the patient. Accordingly, there is a present need for an improved apparatus and method for more closely tracking and compensating a sensor electrical output signal for errors introduced by varying temperatures of the gas mixtures applied to the gas sensor to be analyzed.
Summary of Invention The present invention is an improved, more sensitive, electrochemical gas sensor having improved methods and means for tracking the temperature changes in the gases applied to the sensors for permitting the temperature compensation signals to be rapidly developed and utilized without any time delay, for providing correct, temperature compensated output signals and thereby accurate electrical output signals representative of the concentrations of the electrochemical active gases applied to the gas sensor to be analyzed. The above advantages are produced with small change in the cost of producing the improved gas sensor.
From a structural standpoint, the improved electro-chemical gas sensor includes thermistor means mounted adjacent to an expansion membrane, that is in contact with the gas sensor electrolyte and contains same, in a substantially thermal isolated relationship with respect to the temperature of the gases to be sensed conveyed to the gas sensor so that any change in the temperature of the gas to be sensed is not directly conveyed to the thermistor means whereby the gas sensor and the thermistor means both experience any change in CA 02209784 l997-07-08 11,516 4 1 temperature of the gas to be sensed at substantially the same time whereby said thermistor means provides electrical output signals in response to the sensed temperature changes in the gases being sensed without any substantial time delays between the temperature changes in the gases to be sensed and the electrical output signals provided by the thermistor means.
From a broad method standpoint, the present invention comprehends the provision of an electrochemical gas sensor to provide an electrical output signal in response to the app-lication of a gas mixture to the gas sensor having an electo-chemically active gas to be sensed therein due to the production of a cathodic reaction whereby the electrical output signal is representative of the concentration of the sensed electro-chemically active gas that varies with the temperatures of the gas mixtures thereby resulting in erroneous electrical output signals due to the temperature variations of the gas mixture, mounting thermistor means in the gas sensor in a preselected thermal insulative manner for minimizing any direct heat transfer to the thermistor means so that the gas sensor body and the thermistor means are exposed to the temperature variations of the gas mixture at essentially the same time for thereby permitting accurate compensation of the electrical output signals from the gas sensor, without any time delay, thereby providing accurate output signals of the concentrations of the sensed gases despite temperature variations in the applied gas mixtures.
The method includes the steps of mounting the thermistor means in a heat sink adjacent the gas sensor electrolyte and providing a plurality of thermal insulators stacked in the gas sensor with the thermistor means lead wires spiraled into coils and electrically accessible outside the gas sensor.
11,516 5 1 Brief Descri~tion of the Drawinqs These and other features of the present invention may be more fully appreciated when considered in light of the following specification and drawings, in which:
Fig. l is cross sectional view of a prior art electro-chemical gas senor having thermistor temperature compensation;
Fig. 2 is a graphical illustration of the gas sensor of Fig. 1 electrical output signal variations due to increased temperatures of the gas mixture applied to the gas sensor;
Fig. 3 is a cross sectional view of an electroche~ical gas sensor having means for closely tracking temperature variations of the gas mixtures applied to the gas sensor l-d embodying the present invention;
' Fig. 4 is a view from the top of an unpatted, th~r-istor, looking towards the back side of the gas sensor of Fig. 3 3:1 illustrating the spiral assembly of the thermistor leads, in part illustrated in dotted outline;
Fig. 5 is a side view of the thermistor arrange~en~ .~s viewed in Fig. 4;
Fig. 6 is a detached view of the top of the print.-d circuit board assembly as utilized in the gas sensor of Fi~. 3;
and Fig. 7 is a graphical illustration of the gas sensor of Figs. 3-6 electrical output signal variations due to the increase in the temperature of the gas mixture applied to the gas sensor.
11,516 6 1 Detailed Description of the Preferred Embodiment of the Invention An understanding of the problem of the present day organization of electrochemical gas sensors and the temperature compensation of the sensor electrical output signals by means of thermistor means leads to a better appreciation of the needfor the improvements disclosed herein and the benefits of the novel structures. The electrochemical gas sensor 10 is illustrated in Fig. 1 as a prior art galvanic type of gas sensor for prod-ucing a cathodic reaction at the gas sensing cathode electrode 12 for the gas sensor. The cathodic reaction is produced in response to gas mixtures applied to the gas sensor 10 when the cathode electrode 12 and the associated anode electrode 14 are wet by a suitable electrolyte 16 stored in the container 18 defining the body for the sensor 10. The electrolyte 16 has a preselected volume defined between the thin sensing membrane 20 and the expansion membrane 22 spaced on the opposite side of the anode electrode 14 from the cathode electrode 12. The back side of the container 18 is closed off by the provision of a printed circuit board 24 illustrated spaced from the membrane 22 and mounting a thermistor 26 and a plurality of resistors 28.
An electrical connector 30 is connected to the printed circuit board 24 for deriving the electrical output signals produced by the aforementioned cathodic reaction and'the thermistor signals to be combined for compensating for any temperature changes in the gas mixture applied to the gas sensor 10 in a well known manner. This structure is typical of the prior art galvanic type of electrochemical gas sensors capable of sensing the concentrations of electrochemically active gases, such as oxygen, in the gas mixtures applied to the gas sensor in parts per million. It should be recognized by those skilled in the art that the present invention is also applicable to other types of gas sensors including polarographic type gas sensors.
As illustrated in Fig. 1, the open end of the container 18 is illustrated with an open ended threaded member 32 for recei-ving the gas mixtures applied to the gas sensor 10. This 11,516 7 1 permitS the gas sensor lO to be threaded to a suitable gas block for receiving the gas mixtures flowing through to impinge against the sensing membrane 20. Such a gas block may be constructed of aluminum or plastic. The gas block is diagrammatically illustrated in dotted outline secured to the member 32 in Fig. l. Upon the application of the gas mixture to be analyzed to the gas sensor lO the concentration of the electrochemical active gas in the gas mixture produces a cathodic current that is due to the oxidation or reduction of the active gas providing an electrical current output signal from the sensor lO representative of the concentration of the active gas in the gas mixture. The electrical current can be converted to a voltage output signal by the provision of a suitable output resistor coupled across the output terminalsofthe sensor lO.
A ten ohm resistor mounted on the printed circuit board 24, for example will convert the autput currents to a voltage signal in millivolts. It is also well known that electrical output signals from the gas sensors lO are also dependent on the temp-erature and the temperature variations of the gas mixtures applied to the sensor. The electrical output signals increase in magnitude with the increases in the temperatures of the gas mixture being sensed or analyzed. This change in output signal - is due to the change in the diffusion rate of the applied gas through the thin sensing membrane 20. At the higher gas temp-eratures the output electrical signals increase due to the high diffusion rate of the applied gas through the sensing membrane 20 and thereby the derived output signals erroneously signal the concentration of the sensed active gas in the applied gas mixture. The prior art gas sensors utilized a temperature sensing device in the form of the thermistor 26 mounted on the printed circuit board 24 for the gas sensor lO to provide an electrical output signal representative of the temperature change in the applied gas to the gas sensor. The thermistor output siqnal is utilized as a temperature compensating signal for the erroneously generated sensor output signal to provide the correct 11,516 8 1 output signal compensated for the temperature variations, as well known, without the need for additional corrections.
The thermistor signals are utilized to cancel out the temp-erature components of the sensor generated signals in a known circuit manner. As can be appreciated from viewing Fig. l, the gas mixture to be analyzed is immediately exposed to the thermistor 26 and as a result signals a temperature change that produces an initial low, erroneous output signal from the gas sensor lO. It is known that the gas sensor body takes a time period on the order of 30-40 minutes to change in temperature before it will correctly signal the temperature change in the applied gas mixture. This time delay in pro-viding accurate electrical output signals has been found to be between 30 minutes to one hour. For a patient in a critical care unit wherein the supply of oxygen, for example, is mon-itored this time delay is excessive and the errors introduced with the delayed temperature tracking by the thermistor could be up to 10% of the required oxygen supply and could be detrimental to a patient.
The time delay introduced by the erroneous temperature tracking by the thermistor 26 for the gas sensor lO is graphically illustrated in Fig. 2 for a temperature change from 24 degrees centigrade to 40 degrees centrigade for tests con-ducted on three different gas sensors of the type of gas sensor lO. The space between the vertical lines in Fig. 2 represent 5 minutes in time. All three gas sensors signalled an immediate drop in the value of the electrical output signal due to the thermistor 26 being immediately exposed to the temperature change with a gradual increase in value as the sensor body absorbs the temperature change with time. The electrical output signal reaches asteady state condition after the time delay period required by the sensor body and associated elements to reach the changed temperature, in the above example the 40 de-grees C. This time delay period for the cells of Fig. 2 can be seen to be substantial, on the order of 30 minutes.
11,516 9 1 With the above prior art structures and problems in mind, the improved gas sensor lO' of the present invention will be examined in conjunction with the structures illustrated in Figs. 3-6 and the graphical representation of ~ig. 7. The basic structure of the galvanic type electrochemical gas sensor lO of Fig. l is illustrated in Fig. 3 but illustrating the improved arrangement for sensing the applied gas temperatures and tracking the temperatures without introducing the time delays of the prior art structures. The thermistor 26 in accordance with the present invention is located in very close proximity to the liquid electrolyte adjacent the expansion membrane 22 in a substantially thermally insulated relationship with the gas sensor body and the gases applied to the gas sensor lO' and thereby eliminates the prior art time delays involved in tracking the temperatures of the gases applied to the gas sensors during a change in the temperature of the gases.
To this end, the thermistor 26 is potted to the rear side of the expansion membrane 22 with a heat sink compound 34, such as a zinc oxide or silicone, as illustrated in Fig. 3. In this manner, any change in temperature of the gases undergoing analysis are not directly conveyed to the thermistor 26 to produce -erroneous signal outputs. The lead wires for the thermistor 26 comprise an electrically insulated cable 26C of approximately 3-4 inches in length having the individual lead 2S wires thereof secured to the printed circuit board 24 at the points "4" on the board; see Figs. 4 and 6.
Another important feature of the assembly of the thermistor 26 to the gas sensor 10' is the provision of thermal insulative means arranged between the heat sink compound 34 and the tops of the circuit board devices on the printed circuit board 24 as best illustrated in Figs. 3 and 5. The insulative means, as illustrated, comprises three individual layers of foam stacked upon one another between the heat sink 34 and the printed circuit board 24. The individual layers of foam in-sulation are each a different size and are identified in the 11,516 10 1 drawings as layers 36, 38 and 40 from the top to the bottom, see Fig, 5, in particular. The top most insulative layer 36 is positioned below the thermistor 26 and the heat sink compound 34 and is the smallest in size, diameter wise, of the three insulative layers. The bottom insulative layer 40 is the largest in diameter while the layer 38 is intermediate in size between the diameters of layers 36 and 40. The thickness of the three layers are essentially the same and in combination occupy the volume between the heat sink compound 34 and t!~-' printed circuit board 24. The three layers are arranged in ~
staggered relationship as best seen in Fig. 5. The insula~i~e cable 26C for the thermistor 26 is spiraled or coiled be~ n the insulative layers 36, 38 and 40 between the stacked ~ ~~s, see Figs. 3 and 4, and the individual lead wires of the _l~;e 26C
are connected to point "4" on the printed circuit board ~, as best seen in Fig. 4 and 6.
In the above described manner of insulatively sec_r:n~
the thermistor 26 any changeintemperature of the gas mixt_~s applied to the gas sensor 10' is not directly conveyed to ~e thermistor 26 since the gas sensor container or body 18 bo~
experience the change in gas temperature at essentially th~
same time. Therefore, the electrical output signals develc.-ed by the gas sensor 10' and the thermistor 26 when combined, correctly compensates the sensor generated electrical outp_t signals for the sensed temperature variations so that the resulting temperature compensated electrical output signals are true representations of the signals produced at the gas sensin~
cathode electrode, without any erroneous increases or decrel-,es due to temperature changes.
The gas sensor 10' was tested in the identical mann~?r as the sensor 10 and plotted in Fig. 7 for a temperature chan~e in the sensor applied gas from 24 degrees C. to 40 degrees C.
In Fig. 7, the output signals for six gas sensors are ill~ls~rated as coming to equilibrium right away, without any false incr?ases or decreases in electrical output signals as in the known --ior 11,516 1 art devices.
It should now be appreciated by those skilled in the gas sensor art that the present disclosure has advanced the art for precisely tracking the temperature changes in the gas mixtures applied to the gas sensor so as to provide more sensitive and accurately compensated electrical output signals that better track temperature changes. This tracking results due to the thermistor being responsive to the temperature changes imparted to the liquid electrolyte and not the temperature changes of the sensor body.
Claims (10)
1. In an electrochemical gas sensor for sensing the concentration of an electrochemically active gas, such as oxygen, in a gas mixture to be analyzed and providing sensor electrical output signals representative of the sensed concentrations, said gas sensor comprising an insulative sensor container having an open end and adapted for storing a liquid electrolyte in the container, means for defining a gas sensing cathode electrode supported within the container adjacent said open end of the insulative sensor container, a gas permeable, liquid impermeable membrane secured to said open end of said container in intimate contact with the cathode electrode and having a preselected thin thickness for limiting the diffusion of the gases to be sensed and to be conveyed to said cathode, an expansion membrane mounted within said sensor container and being spaced a preselected distance from said open end and for storing an electrolyte in the volume between said gas permeable membrane and the expansion membrane, a liquid electrolyte stored in the volume between said gas permeable membrane and the expansion membrans, means for defining an anode electrode mounted in the electrolyte adjacent the expansion membrane, the improvement comprising thermistor means mounted adjacent to the expansion membrane in a substantially thermal isolated relationship with respect to the temperature of the gases to be sensed that are conveyed to said gas permeable membrane so that any change in the temperature of the gas to be sensed is not directly conveyed to the thermistor means whereby the sensor and the thermistor means both experience any change in temperature of the gas to be sensed at substantially the same time whereby said thermistor provides electrical output signals in response to the sensed temperature changes without any substantial time delays between the temperature changes and the thermistor electrical output signals useful for temperature compensation of said sensor electrical output signals.
2. In an electrochemical gas sensor of the type defined in claim 1 wherein said thermistor means is secured to said expansion membrane with a thermal insulator so as to be substantially sensitive only to temperature changes of said electrolyte for providing temperature compensation signals for the output signals generated by said gas sensor.
3. In an electrochemical gas sensor of the type defined in claim 2 wherein said thermistor means is secured to said expansion membrane with heat sink means and further including a printed circuit board for enclosing the end of said insulative container opposite to said open end thereof, a plurality of thermal insulators stacked between said thermistor means and said printed circuit board for minimizing any direct heat transfer from said gases to be sensed to the thermistor means, said thermistor means having an insulated electrical cable spiraled between said stacked thermal insulators and connected to said circuit board.
4. In an electrochemical gas sensor of the type defined in claim 3 wherein said plurality of thermal insulators comprise individual insulators of different sizes that increase in size from adjacent said thermistor means to said printed circuit board.
5. In an electrochemical gas sensor of the type defined in claim 3 wherein said plurality of thermal insulators comprise three thermal insulators stacked between said thermistor means and the printed circuit board, the thermal insulator adjacent said thermistor means being the smallest insulator and the largest insulator being adjacent said circuit board, and the third insulator being of a size larger than the smallest insulator and smaller than the largest insulator and stacked intermediate the small and large insulators, said insulated thermistor having lead wires spiraled into coils of increasing diameter betwen the small and third insulators and between the large and third insulators and being electrically connected to said circuit board.
6. A method of compensating an electrochemical gas sensor for sensing the concentration of an electrochemically active gas such as oxygen in a gas mixture to be analyzed due to changes in temperature of the gas-mixture-applied to the electrochemical gas sensor, said gas sensor providing electrical output signals representative of concentration of the sensed, active gas due to the resulting cathodic reaction that is compensated for any temperature changes in the applied gas mixture, the method including the steps of providing an electrochemical gas sensor having a gas sensing cathode and anode wet by an electrolyte and adapted to provide an electrical output signal in response to the application of a gas mixture having an electrochemically active gas to be sensed therein to said gas sensing cathode due to the production of a cathodic reaction whereby the electrical output signal is representative of the concentration of the sensed electrochemically active gas, said electrical output signal being further characterized as varying with the variations in temperature of the gas mixture applied to said sensor resulting in erroneous electrical output signals due to the temperature variations, mounting thermistor means in the sensor in a pre-selected thermal insulative manner for minimizing any direct heat transfer to said thermistor means whereby said gas sensor and said thermistor means are exposed to temperature changes of the gas being sensed at essentially the same time permitting compensation of the electrical output signals from said sensor without time delay and thereby providing accurate temperature compensation output signals with the tempurature variations of the gas undergoing sensing representative of the true sensed gas concentrations.
7. A method of compensating an electrochemical gas sensor for sensing the concentration of an electrochemically active gas such as oxygen in a gas mixture to be analyzed due to changes in temperature of the gas mixture applied to the electrochemical gas sensor, said gas sensor providing electrical output signals representative of concentration of the sensed, active gas due to the resulting cathodic reaction that is compensated for any temperature changes in the applied gas mixture, as defined in claim 6 the method including the steps of providing an electrochemical gas sensor having an insulative container storing a gas sensing cathode, an anode and an electrolyte wetting the cathode and anode for producing a cathodic reaction upon the application of an electrochemically active gas to the gas sensing cathode arranged in the insulative sensor container with a preselected volume of electrolyte, mounting a temperature sensitive resistor in the insulative sensor container immediately adjacent the volume of electrolyte for closely tracking the variations in temperature of gases to be sensed for providing temperature compensation signals in response to the temperature variations, without any time delays, for combination with the electrical output signals provided by the gas sensor whereby the combination of the compensation signals and electrical output signals provide compensated electrical output signals accurately representative of the concentrations of the sensed active gases in the gas mixture applied to the gas sensor.
8. A method of compensating an electrochemical gas sensor for sensing the concentration of an electrochemically active gas in a gas mixture applied to the sensor for temperature changes, the gas sensor providing electrical output signals representative of the sensed electrochemically active gas that vary with the temperature variations of the applied gas mixture, the method includes the steps of providing an electrochemical gas sensor having an insulative container having a gas sensing cathode electrode and an anode electrode mounted in the container with an electrolyte, said container having an open end adjacent the cathode electrode for applying the gas mixture to the cathode electrode and an expansion membrane mounted to said container in a preselected spaced relationship with said open end of the container and containing the electrolyte, mounting thermistor means on the expansion membrane to be responsive to temperature changes in the electrolyte, securing the thermistor means to the expansion membrane with heat sink means so as to substantially prevent any temperature changes from being directly transmitted to the thermistor means so that said gas sensor and the thermistor means both respond to any temperature changes at substantially the same time, mounting thermal insulative means on the opposite side of the thermistor means from the side secured to the expansion membrane, the thermistor means including insulated lead wires extending therefrom for deriving temperature compensating electrical signals from said gas sensor, and arranging said leads with said thermal insulative means so as to be contained within said insulative means to prevent temperature changes to be conducted to said thermistor means and to be accessible outside of the gas sensor.
9. A method of compensating an electrochemical gas sensor as defined in claim 8 wherein the step of mounting thermal insulative means includes the steps of stacking a plurality of thermal insulative means, each a different, pre-selected size, for thermally insulating the thermistor means, and spiralling said lead wires of the thermistor means in an insulative relationship between each of the stacked, plurality of insulative means and arranged to be accessible externally of the gas sensor.
10. A method of compensating an electrochemical gas sensor as defined in claim 9 wherein the step of spiralling the lead wires comprises wrapping the lead wires in a coiled configuration between the stacked insulative means.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/683,985 | 1996-07-19 | ||
| US08/683,985 US5788832A (en) | 1996-07-19 | 1996-07-19 | Temperature compensated electrochemical gas sensor and method for closely tracking the temperature variations of a gas to be sensed |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2209784A1 true CA2209784A1 (en) | 1998-01-19 |
Family
ID=24746250
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002209784A Abandoned CA2209784A1 (en) | 1996-07-19 | 1997-07-08 | An improved temperature compensated electrochemical gas sensor and method for closely tracking the temperature variations of a gas to be sensed |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US5788832A (en) |
| EP (1) | EP0819936B1 (en) |
| JP (1) | JPH10115600A (en) |
| KR (1) | KR980010414A (en) |
| AR (1) | AR007921A1 (en) |
| CA (1) | CA2209784A1 (en) |
| DE (1) | DE69721653T2 (en) |
| SG (1) | SG66380A1 (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6265750B1 (en) | 1999-07-15 | 2001-07-24 | Teledyne Technologies Incorporated | Electrochemical gas sensor and method of making the same |
| DE10007396C2 (en) * | 2000-02-18 | 2003-04-10 | It Dr Gambert Gmbh | Device for the adjustment of galvanic sensors |
| KR100497991B1 (en) * | 2002-07-29 | 2005-07-01 | 세주엔지니어링주식회사 | Portable gas detector and re-calibration method thereof |
| US7140232B2 (en) * | 2002-12-16 | 2006-11-28 | Radiodetection Limited | Method and apparatus for multiple gas sensor |
| DE102004002034A1 (en) | 2004-01-14 | 2005-08-11 | Bernhard Engl | Device for mixed gas supply in Kreislaufatemgeräten |
| US20060203886A1 (en) * | 2005-03-10 | 2006-09-14 | Aai Corporation | Simplified thermal isolator for temperature sensor |
| US7664607B2 (en) | 2005-10-04 | 2010-02-16 | Teledyne Technologies Incorporated | Pre-calibrated gas sensor |
| JP4974304B2 (en) * | 2007-10-29 | 2012-07-11 | 日本特殊陶業株式会社 | Sensor control device |
| JP6126852B2 (en) | 2012-02-21 | 2017-05-10 | ハウメット コーポレイションＨｏｗｍｅｔ Ｃｏｒｐｏｒａｔｉｏｎ | Gas turbine component coating and coating method |
| US10175254B2 (en) | 2013-07-16 | 2019-01-08 | Palo Alto Health Sciences, Inc. | Methods and systems for quantitative colorimetric capnometry |
| GB201719769D0 (en) * | 2017-11-28 | 2018-01-10 | Cronin 3D Ltd | Analytical device and methods of use |
| US11415491B2 (en) * | 2018-09-27 | 2022-08-16 | Apple Inc. | Pumping mechanism for gas sensors |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3351544A (en) * | 1964-03-23 | 1967-11-07 | Honeywell Inc | Gas detecting cell with detachable unit |
| AT272273B (en) * | 1965-12-13 | 1969-07-10 | Ceskoslovenska Akademie Ved | Measuring electrode arrangement for the determination of gases dissolved in liquids |
| US3510421A (en) * | 1967-06-12 | 1970-05-05 | Honeywell Inc | Polarographic cell |
| US3767552A (en) * | 1971-10-06 | 1973-10-23 | Teledyne Ind | Gas analyzer |
| DK135475B (en) * | 1973-03-22 | 1977-05-02 | Radiometer As | Electrochemical measuring probe for polarographic measurements with temperature compensation. |
| DK143246C (en) * | 1978-03-28 | 1981-11-30 | Radiometer As | ELECTRIC DEVICE FOR TRANSCUTAN P (CO2) MEASUREMENT |
| US4367133A (en) * | 1980-07-02 | 1983-01-04 | Comsip, Inc. | Electrochemical gas analyzer |
| US4466878A (en) * | 1983-01-12 | 1984-08-21 | Instrumentation Laboratory Inc. | Electrochemical electrode assembly |
| JPS59174748A (en) * | 1983-03-25 | 1984-10-03 | Hitachi Ltd | Apparatus for measuring concentration of dissolved gas |
| US4495051A (en) * | 1983-09-30 | 1985-01-22 | Japan Storage Battery Company Limited | Galvanic cell type oxygen sensor |
| US5085759A (en) * | 1989-11-13 | 1992-02-04 | Duncan Instrument Company | Apparatus for rapid biological oxidation demand of liquids |
| DK95792A (en) * | 1992-07-24 | 1994-01-25 | Radiometer As | Sensor for non-invasive, in vivo determination of an analyte and blood flow |
-
1996
- 1996-07-19 US US08/683,985 patent/US5788832A/en not_active Expired - Lifetime
-
1997
- 1997-07-08 CA CA002209784A patent/CA2209784A1/en not_active Abandoned
- 1997-07-09 DE DE69721653T patent/DE69721653T2/en not_active Expired - Lifetime
- 1997-07-09 EP EP97305025A patent/EP0819936B1/en not_active Expired - Lifetime
- 1997-07-15 KR KR1019970032706A patent/KR980010414A/en not_active Application Discontinuation
- 1997-07-18 JP JP9193765A patent/JPH10115600A/en active Pending
- 1997-07-18 SG SG1997002502A patent/SG66380A1/en unknown
- 1997-07-18 AR ARP970103235A patent/AR007921A1/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| EP0819936A1 (en) | 1998-01-21 |
| DE69721653T2 (en) | 2004-03-25 |
| KR980010414A (en) | 1998-04-30 |
| SG66380A1 (en) | 1999-07-20 |
| AR007921A1 (en) | 1999-11-24 |
| US5788832A (en) | 1998-08-04 |
| EP0819936B1 (en) | 2003-05-07 |
| DE69721653D1 (en) | 2003-06-12 |
| JPH10115600A (en) | 1998-05-06 |
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